Process for preparing n-actyl-o-hydrocarbylphosphoroamidothioate metal salts

ABSTRACT

S-ammonium (or metal) salts of N-acyl-Ohydrocarbylphosphoroamidothioates are prepared by reacting an Nacyl-O,O-dihydrocarbylphosphoroamidothioate with an ammonium (or metal) sulfide or polysulfide.

United States Patent [191 Franke PROCESS FOR PREPARING N-ACTYL-O-HYDROCARBYLPHOS-- PHOROAMIDOTHIOATE METAL SALTS [75} Inventor: Hans G. Franke, Orinda, Calif.

[73} Assignee: Chevron Research Company. San

Francisco, Calif.

[22} Filed: June 17, 1974 [2]] App]. No.: 479,970

Related U.S. Application Data [63] Continuation-impart of Ser. No. 317,479, Dec. 21,

1972, Pat. NO. 3,832,425.

[52] U.S. Cl. 260/987 [51] Int. Cl? C07F 9/24 [58] Field of Search 260/987 July 22, 1975 [56] References Cited UNITED STATES PATENTS 3,662,034 5/1972 Oswatd et a] 260/987 X Primary ExaminerAnton H. Sutto Attorney, Agent, or Firm--J. A. Buchanan, Jr.; John Stoner, Jr.; Raymond Owyang [57] ABSTRACT 9 Claims, N0 Drawings PROCESS FOR PREPARING N-ACTYL-O-I-IYDROCARBYLPI'IOS- PHOROAMIDOTI'IIOATE METAL SALTS -c-R PC I CROSSREFERENCE To RELATED APPLICATION 5 wherein R is alkyl, alkenyl or alkynyl of up to 6 carbon This application is a continuation-in-part of application Ser. No. 317,479, filed Dec. 21, 1972, now US. Pat. No. 3,832,425.

BACKGROUND OF THE INVENTION US. Pat. No. 3,676,555, issued to G. Schrader et al discloses that compounds having the general formula wherein R is alkyl are excellent insecticides. These compounds are prepared from S-sodium-O-alkylphosphoroamidothioate by reaction with a methylating agent such as methyl iodide. The sodium salt, in turn, is obtained by the reaction of sodium hydroxide with an 0.0-dialkylphosphoroamidothioate as illustrated in the following equation (1):

wherein R is alkyl.

Unfortunately, the insecticides of formula (I) have relatively high mammalian toxicity and are therefore of limited use. U.S. application, Ser. No. 13,846, filed Feb. 24, 1970, now US. Pat. No. 3,716,600, discloses that N-acylated derivatives, e.g., N-acetyl, of the compounds of formula (I) are of essentially equal insecti' cidal activity but are significantly less toxic to mammals. However, it has been found by experimentation that preparation of the new and safer insecticides of US. Ser. No. 13,846 from the sodium salt of the corresponding N-acylated phosphoroamidothioate was not possible because the sodium salt would not form upon the reaction of an 0,0-dialkyl-N-acylphophororamidothioate with sodium hydroxide. Under mild conditions only starting material was recovered; and under more forcing conditions, degradation occurred without the formation of the desired sodium salt.

SUMMARY OF THE INVENTION It has now been found that an S-ammonium (or metal) salt is formed from an 0,0-dihydrocarbyl-N- acylphosphoroamidothioate by reaction with an ammonium (or metal) sulfide or polysulfide.

DESCRIPTION OF THE INVENTION The 0,0-Dihydrocarbyl-N-acylphosphoroamidothioate Reactant The 0,0-dihydrocarbyl-N-acylphosphoroamidothioate reactant employed in the process of the invention is represented by the following formula (IV) atoms, R has up to I8 carbon atoms and is hydrogen, alkyl, alkenyl, phenyl, aralkyl or alkaryl substituted with up to 3 fluorine, chlorine or bromine atoms or with up to 1 alkoxy or alkylthio of 1 to 4 carbon atoms, and R is hydrogen or alkyl of l to 6 carbon atoms.

Representative alkyl groups which R and R may represent include methyl, ethyl, propyl, isopropyl, butyl, sec-pentyl and hexyl. Representative R alkenyl groups of 2 to 6 carbon atoms include vinyl, allyl, 2- butenyl, 3-butenyl, 2-hexenyl, S-hexenyl, etc. REpresentative R alkynyl groups of 3 to 6 carbon atoms include Z-propynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 5- hexynyl, etc. The R groups of formula (IV) may be the same or different. The preferred R group is alkyl of I to 3 carbon atoms, especially methyl. The preferred R group is hydrogen.

Representative alkyl R groups are methyl, ethyl, propyl, isopropyl, sec-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, pentadecyl, octadecyl, etc. Representative alkenyl R groups are allyl, 2-butenyl, 5- hexenyl, 9-decenyl, l4-pentadecenyl, etc. Representative aralkyl R groups are benzyl, Z-phenylethyl, 3-(0- tolyl)propyl, 4-phenylhexyl, 6-(o-tolyl)hexyl, etc. Representative alkaryl R groups are o-tolyl, p-tolyl, 2,4-dimethylphenyl, 3,5-diisopropylphenyl, 4-t-butylphenyl, etc.

Representative halo-, alkoxyand alkylthiosubstituted R groups include haloalkyl groups such as fluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, tetrachloroethyl, 3-chloropropyl, 4- bromobutyl, IO-chlorodecyl, l4-bromotetradecyl, etc; haloalkenyl such as trichlorovinyl, 2,2-difluorovinyl, 2-bromo-9-decenyl, etc; haloaryl groups such as 4- chlorophenyl, 2,4-difluorophenyl, 3,5-dibromophenyl, 4-chlorobenzyl, 2-chloro-4-methylphenyl, etc.; alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, 2- ethoxyethyl, 4-butoxybutyl, etc.; alkoxyalkenyl such as 4-methoxy-2-butenyl, 5-ethoxy-3-pentenyl, etc.; alkoxyaryl such as 4-methoxyphenyl, 2-methoxy-4- methylphenyl, 3-propoxyphenyl, 2-(2-methoxyphenyl- )ethyl, etc.; alkylthioalkyl such as methylthiomethyl, ethylthiomethyl, Z-ethyIthioethyl, S-pentyIthiopentyI, etc.; alkylthioalkenyl such as 4-methylthio-2-butenyl, 4-ethylthio-3-hexenyl, etc.; alkylthioaryl such as 4- methylthiophenyl, Z-ethyIthiobenzyl, 3-methyl-4- methylthiophenyl, 4-(Z-methylthiophenyl)butyl, etc. The most preferred R groups are alkyl of l to 6 carbon atoms, especially methyl.

Preferred R groups have up to 12 carbon atoms. Most preferred R groups are alkyl of l to 12 carbon atoms and alkoxyalkyl of 2 to 12 carbon atoms.

The compounds of formula (I) may be prepared by acylating an 0,0-dihydrocarbylphosphoroamidothioate with an appropriate acylating agent, e.g., an acid halide (VI) or acid anhydride (VII), as depicted in the following equation (2) wherein R, R and R have the same significance as previously defined.

The acylation reaction (2),is usually carried out at about O60C in the presence of solvent such as meth ylene dichloride, chloroform, tetrahydrofuran and benwherein R and R have the same significance as previously defined.

The first two reactions (equations 3-4) of the synthesis involve the addition of 2 mols of the alcohol (Vlll) to 1 mol of phosphorous thiochloride (PSCl (if both R are the same, a single reaction can be carried out). These reactions are preferably carried out in the presence of a weak base, such as the organic amines, for example pyridine, dimethylaniline, triethylamine, etc. The base is preferably present in an amount at least equal to the mols of alcohol. An inert organic solvent, such as diethyl ether, tetrahydrofuran, dioxane, dichloromethane, etc. may be present. The reaction temperatures are generally in the range of to C., preferadihydrocarbyl of the reaction is indicated by cessation of ammonium chloride or amine hydrochloride precipitation. Following the reaction,.the product (V) can be isolated by conventional methods such as filtration, extraction, distillation, chromatography, etc.

The Sulfide and Polysulfide Reactant Ammonium sulfide and polysulfide, e.g. (N l-L0 8 wherein x is l to 5, of reasonable purity are suitably employed in the process of the invention. Commerciallyavailable aqueous solutions of ammonium sulfide or polysulfide are particularly suitable for use in the process. v

Metal sulfides and polysulfides suitably employed in the process of the invention include alkali metal, e.g., lithium, sodium, or potassium and alkaline earth metal, e.g. calcium or barium, sulfides.

Ammonium sulfide and polysulfide are preferred over metal sulfides in the process of the invention.

The Reaction Conditions The process of the invention is suitably conducted in the liquid phase in the presence or absence of an inert solvent which is liquid at reaction temperature and pressure. Suitable organic solvents include oxygenated hydrocarbons such as alkanols of l to 6 carbon atoms, e.g., methanol, ethanol, isopropanol, butanol, hexanol, etc.; dialkyl ketones of up to 8 carbon atoms, e.g., acetone, methyl ethyl ketone, etc.; acyclic alkyl ethers, e.g., dimethyl ether, di-butyl ether, dimethoxyethane, diethylene glycol dimethyl ether, etc.;; and cycloalkyl ethers, e.g., dioxane, tetrahydrofuran and tetrahydropyran. Other suitable organic solvents include nitriles such as acetonitrile and propionitrile; and dialkylamides such as dimethylformamide; dialkylsulfoxides such as dimethyls ulfoxide. Still other suitablesolvents comprise water or water containing a portion of a polar organic co-solvent. Suitable mixtures of water and a polar organic co-solvent vary by volume, from about 20 to co-solvent and from about 20 to 80% water. Solvents are used in quantities sufficient to form a slurry of the reactants or a substantially liquid-phase solution. Generally, up to mols of solvent per mol of the N-acylphosphoroamidothioate is employed. I The process is preferably conducted in the presence of a solvent, and the preferred solvent is water or a mixture of water and a polar organic solvent.

The temperature of the reaction may vary from about 10 to 100C, preferably from 25 to 75C. Pressure is not critical, so long as the reaction mixture is maintained substantially in a non-gaseous phase. Typical pressures vary from 1 to 10 atmospheres. The time of reaction varies with the temperature. In general, the reaction is complete within 10 hours, more usually within 5 hours or less.

The molar ratio of ammonium (or metal) sulfide or polysulfide to N-acylphosphoroamidothioate varies from about 1:2 to 10:1, preferably from about l:2 to 2:1.

The process of the invention produces as by-products hydrocarbyl mercaptans, dihydrocarbyl sulfides and/or polysulfides, e.g., RSl-l, RSR or RSSR wherein R has the same significance as previously defined. It has been found that the additional presence of sulfur and/or ammonia as reaction components results in the formation of principally dihydrocarbyl disulfide by-products. When sulfur or ammonia is employed, the molar ration of sulfur (or ammonia) to ammonium (or metal) sulfide or polysulfide varies from about 5:1 to 1:5, preferably from about 2:1 to 1:2.

The precise method of contacting the reactants employed in the process of the invention is not critical. In the preferred modification, the sulfide or polysulfide, the N-acylphosphoroamidothioate and solvent (and sulfur or ammonia, if any) are maintained with agitation at reaction temperature and pressure for the desired reaction period. The S'salt of the N-acylphosphoroamidothioate is sometimes soluble in the reaction medium and may be used for further reactions without separation. However, the product usually precipitates upon standing as a solid crystalline material which may be collected by filtration, centrifugation or decantation. The solid product can be purified by washing with a liquid or by crystallization from an appropriate solvent such as acetone, ethanol, etc.

The Metal and Ammonium Phosphoroamidothioate Salts The S-metal and S-ammonium salts produced by the process of the invention are represented by the formula (XII) o MS\T wherein R R and R have the same significance as previously defined and M is ammonium or a metal cation, e.g., an alkali or alkaline earth metal cation.

Illustrative S-metal and S-ammonium salts of formula (XII) are S-ammonium-N-acetyl-O-methylphosphoroamidothioate, S-ammonium-N-crotonoyl-O- ethylphosphoroamidothioate, S-ammonium-N- trichloroacetyl-N-methyl-O-propylphosphoroamidothioate, S-lithium-N-methoxyacetyl-O-methylphos phoroamidothioate, S-lithium-N-4-chlorocrotonyl-O- butylphosphoroamidothioate, S-lithium-N-4- alkoxybenzoyl-O-methylphosphoroamidothioate, S- lithium-N-3-phenylpropionyl-O-methylphosphoroarnidothioate, S-sodium-N-hexanoyl-O- methylphosphoroamidothioate (m.p. lO5-108C), S- sodium-N-isovaleryl-O-methylphosphoroamidothioate (mp 1 -I I 8C), S-sodium-N-acetyl-N-isopropyl-O- methylphosphoroamidothioate, S-sodium'N- methoxyacetyl-O-methylphosphoroamid hioate, S- sodium-N-propionyl-O-methylphosphor amidothioate, S-sodium-N-methylthioacetyl-O-methylphosphoroamidothioate, S-sodium-N-butyryl-O- methylphosphoroamidothioate, S-sodium-N-octanoyl- O-methylphosphoroamidothioate, S-sodium-N- decanoyl-O-methylphosphoroamidothioate, Ssodium- N-dichloroacetyl-O-methylphosphoroamidothioate, S-potassium-N-acetyl-O-ethylphosphoroamidothioate, S-sodium-N-ethoxyacetyl-O-ethylphosphoroamidothioate, S-potassium-N-fluoroacetyl-N-isopropyl-O- hexylphosphoroamidothioate, S-potassium-N- cthylthioacetyl-O-methylphosphoroamidothioate, S- potassium-N-propionyl-O-methylphosphoroamidothioate, S-potassium-N-4-methylbenzoyl-O-methylphosphoroamidothioate, S-calcium-Nacetyl-O- methylphosphoroamidothioate, S-calcium-N- methoxyacetyl-O-methylphosphoroamidothioate, S-

6 barium-N-acetyl-O-methylphosphoroamidothioate, S- barium-N-4-methoxybutyryl-O-methylphosphoroamidothioate, etc.

The preferred salts of formula (VI) are those wherein M is sodium, potassium or ammonium and R is alkyl or alkoxyalkyl. The most preferred salts are N- alkanoylphosphoroamidothioates wherein M is ammonium, R is alkyl of l to 11 carbon atoms, and both R are the same. The ammonium salts are preferred in part because they are substantially less hydroscopic than the corresponding metal salts.

The metal and ammonium salts prepared by the process of this invention are useful intermediates for the preparation of O-hydrocarbyl-S-alkylor alkenyl-N- acylphosphoroamidothioates. They are especially useful in the preparation of compounds having different groups attached to the sulfur and oxygen atoms. These derivatives are prepared by reacting the salt with an alkylating agent. Suitable alkylating agents include the alkyl and alkenyl halides of up to 10 carbon atoms, such as methyl iodide, ethyl bromide, allyl chloride, hexyl bromide, crotyl chloride, benzyl chloride, propargyl bromide, isopropyl iodide, etc,; the dialkyl and dialkenyl sulfates of up to 10 carbon atoms, such as dimethyl sulfate, diethyl sulfate, diallylsulfate, etc.; and the alkyl and alkenyl arylor alkenesulfonates, such as methyl p-toluene sulfonate, ethyl 2,4-xylenesulfonate, allyl p-toluenesulfonate, methyl methanesulfonate, allyl methanesulfonate, etc. The preferred alkylating agents are the dialkyl sulfates, especially the dimethyl sulfate.

Alkylation is effected by mixing the S-salts of the N acylated phosphoroamidothioates and the alkylating agent in an inert solvent or in excess of liquid alkylating agent at temperatures in the range of 080C, preferably 2560C. Suitable solvents are the halogenated hydrocarbons such as dichloromethane, chloroform, tetrachloroethane, or acetonitrile, acetone, methanol, etc. The preferred solvent is water.

EXAMPLES The following examples illustrate the variations in the process of making S-salts of N-acylphosphoroamidothioates.

EXAMPLE 1 Preparation of S-ammonium-O-methyl-N-acetylphosphoroamidothioate S-ammonium-O-methyl-N-acetylphosphoroamidothioate was prepared in a series of experiments by reacting 0,0-dimethyl-N-acetylphosphoroamidothioate with ammonium sulfide in aqueous reaction medium under a variety of reaction conditions, including the presence of sulfur and/or ammonia as additional reactants. Each experiment was conducted by contacting the reactants in aqueous reaction medium for the indicated reaction time at the indicated temperature. The reaction mixture was then evaporated at low tempera ture under reduced pressure to give the ammonium salt product. The ammonium salt is then purified by washing with an inert solvent such as acetonitrile and dried.

The ammonium salt is characterized by a melting point of greater than 220C and a nuclear magnetic resonance spectrum having a doublet at 3.55 8, J=l 3 cps, (3H) and a doublet at 2.06 6, J=l cps, (3H).

The reactants employed, the reaction conditions and the yield of S-ammonium salt are tabulated in Table 1.

ple l. The reaction conditions and results are tabulated in Table 11.

TABLE 11 M01 M01 M01 Temp. Time Yield Run P Compd. (NH S, H O C Hr. NH, Salt TABLE I M01 M01 Mol M01 M01 Temp. Time Yield Run P Compd (NI-19 Sulfur NH Water C Hr. NH, Salt 1 0.046 0.05 0 0.7 55 3 97 2 0.1 0.1 0 0 1.4 45 2 97.5 3 0.046 0.05 0 0 0.7 55 1.5 99 4 0.1 0.075 0 0 1.1 55 2 75 0.046 0.025 0 0 0.35 55 3 64 6 0.2 0.2 0.15 0 1.8-2.2 50 2 100 7 0.2 0.18 0.15 0 1 8-2.2 50 2 98.3 8 0.2 0.16 0.15 0 1.8-2.2 50 2 99 9 0.2 0.14 0.15 0 l 82.2 50 2 100 10 0.2 0.12 0.15 0 l 8-2.2 50 2 98.4 11 0.2 0.12 0.15 0 1 8-2.2 50 2 99.5 12 0.2 0.10 0.15 0 l 82.2 50 2 87.3 13 0.2 0.10 0.15 0 l 82.2 50 2 84.4 14 0.2 0.10 0.15 0 1.8-2.2 2 87.1 15 0.2 0.10 0.15 0 2 40 2 91.3 16 0.12 0.06 0.15 0 2 40 2 100 17 0.2 0.1 0.15 0.04 2 40 2 95.6 18 0.2 0.1 0.15 0.2 2 40 2 94.6

0.0dimcKhyIN-acetylphosphor0amidolhioale EXAMPLE 2 EXAMPLE 4 Preparation of S-methyl-O-methyl-N-acetyl Preparation of Metal Salts of phosphoroamidothioate S-ammonium-O-methyl-N-acetylphosphoroamidothioate was prepared by a procedure similar to that of Run 1, Example 1, except that the ammonium salt was not isolated. Instead the ammonium salt-containing reaction mixture was acidified with sulfuric acid to pH EXAMPLE 3 Preparation of S-ammonium-O-methyl-N-acetyl phosphoroamidothioate S-ammonium-O-methyl-N-acetylphosphoroamidothioate was prepared in a series of experiments by reacting 0,0-dimethyl-N-acetylphosphoroamidothioate with ammonium polysulfide [52% (Ni-10 where x is l to 5] in aqueous reaction medium. Each experiment was conducted by a procedure similar to that of Exam- O-methyl-N-acetylphosphoroamidothioate Alkali and alkaline earth metal salts of O-methyl-N- acetylphosphoroamidothioate were prepared in a series of experiments by reacting 0,0-dimethyl-N- acetylphosphoroamidothioate with alkali and alkaline earth metal sulfides. Each experiment was conducted by contacting the reactants for the indicated reaction time at the indicated temperature. The reaction mixture was then evaporated at low temperature under reduced pressure to give metal salt product. The metal salt is then purified by washing with acetonitrile and dried. The reactants employed, the reaction conditions and the results are tabulated in Table 111.

TABLE l1l-Continued M01 P Sulfide Solvent Temp. Time Yield Run Com- (mol) (mol) C Hrs. S-Salt pound (0.1) (2.8) 8 0.1 K S H 100 2 100 0.2 mol NH4CI used as additional reactant EXAMPLE Preparation of S-ammonium-O-methy1-N-acetylphosphoroamidothioate S-ammonium-O-methyl-N-acetylphosphoroamidothioate was prepared in a series of experiments by reacting 0.0dimethyl-N-acetylphosphoroamidothioate with ammonia (or ammonium hydroxide or acetate) under a variety of reaction conditions. In runs 9, and 14 hydrogen sulfide (0.150.l6 mol) was added as an additional reactant. Each experiment was conducted by contacting the reactants at the indicated temperature for the indicated reaction period. The reaction mixture was then evaporated at low temperature under reduced pressure to give the ammonium salt product. The ammonium salt is then purified by washing with an inert solvent such as acetonitrile and dried. The reactants employed, the reaction conditions and the results are tabulated in Table IV.

EXAMPLE 7 Hygroscopicity of S-ammonium-O-methyl-N-acetylphosphoroamidothioate A 3.195 g. sample of S-ammonium-O-methyl-N- acetylphosphoroamidothioate was stored in a desiccator containing a reservoir of water at 25C. After 24 hours, the weight of the sample increased by 1.2%. In a similar experiment with S-sodium-O-methyl-N- acetylphosphoroamidothioate, the weight of the sample increased by 11.1%.

EXAMPLE 8 A solution of 5.5 g. (0.03 mol) 0,0-dimethyl-N- acetylphosphoroamidothioate, 2.4 g. (0.03 mol) of 50% aqueous sodium hydroxide solution and 15 ml. of methanol was allowed to stand at about 25C for about 26 hours. The solution was evaporated under reduced TABLE IV M01 M01 Solvent Temp. Time Yield Run P Compd.* NH: (Mel) "C Hr. NH. Salt 1 2.54 3 neat -50 3 30 2 0.25 3 CHzClg reflux 5 0 (0.78) 3 0.36 0.88 CH OH -48 1.3 3 (1.25) 4 0.147 0.70 DME 75 3.5 57

(0.2) 5 0.55 3.5 DME 65 4.5 72 (0.28) 6 0.041 0.05 DME 3 45 (0.028) 7 0.041 0.05 DME 4045 40 33 (0.028) 8 0.13 1.2 Dioxane 65 3 51 (0.18) 9 0.1 0.3 DME 55 1 5 (0.47) 10 0.1" 0.3 C H OH 55 1.5 58 (0.87)

1 1 0.038 0.82" H O" 55 2.5 38 12 0.11 0.8" CH OH 23 48 23 13 0.11 0.45" DME 25 2 weeks 0 (0.28)

15 0.114 0.114" neat 3 0 '0,0-dimethyl-N-ucetylphosphoroamidothioate "Dimethoxyerhane 0.15-0.16 mol H,S used as additional reactant "Concentrated aqueous NH OH "Ammonium acetate EXAMPLE 6 A mixture of 12.3 g (0.05 mol) 0,0-dimethy1-N- methoxyacetylphosphoroamidothioate, 6.5 g. of 52% wt. aqueous ammonium sulfide solution (0.05 mol ampressure to give a viscous oil. When the oil was diluted with acetone, no sodium salt precipitate was obtained.

11 ous mixture was extracted with methylene dichloride. The methylene dichloride extracts were washed with water, dried over magnesium sulfate and evaporated under reduced pressure to give a yellow oil. Infrared EXAMPLE 9 A solution of 11 g. (0.06 mol) 0,0-dimethyll lacetylphosphoroamidothioate, 4.8 g. (0.06 mol) of 50% aqueous sodium hydroxide solution and 30 ml. methanol was refluxed for 2 hours. The solution was evaporated under reduced pressure to give a semisolid residue. The residue was diluted with acetone and filtered to give 1.6 g. of a solid. Analysis of the solid for S-sodium-O-methyl-N-acetylphosphoroamidothioate (C l-l NO PSNa) showed:

Calc. Found N 7.33 Trace P 16.20 trace S 16.78

EXAMPLE Preparation of S-methyl-O-methyl-N-acetylphosphoroamidothioate A 6.6-g (0.052 mol) sample of dimethyl sulfate was added to a solution of 5.0 g (0.026 mol) S-sodium-O- methyl-N-acetylphosphoroamidothioate in 15 ml of water. The reaction mixture (mild exotherm) was stirred at ambient temperature (25-35C.) for 3 hours. The reaction mixture was evaporated, diluted with methylene chloride and filtered to give 4.8 g of S-methyl-O-methyl-N-acetylphosphoroamidothioate.

What is claimed is:

1. A process for preparing S-metal salts of N-acylphosphoroamidothioates which comprises reacting an N-acylphosphoroamidothioate of the formula wherein R individually is alkyl, alkenyl, or alkynyl of up to 6 carbon atoms, R has up to 18 carbon atoms and is hydrogen, alkyl, alkenyl, phenyl, aralkyl or alkarylsubstituted with up to 3 fluorine, chlorine or bromineatoms or with up to l alkoxy or alkylthio of l to 4 carbon atoms, and R is hydrogen or alkyl-of l to 6 carbon atoms, with an alkali or alkaline earth metal sulfide or polysulfide and from 0.2 mol to '5mols of sulfur permol of sulfide or polysulfide, in liquid phase at a temperature of about 10C to l25Cp 2. The process of claim 1 wherein the process is conducted in aqueous solution.

3. The process of claim 2 wherein the sulfide or polysulfide is an alkali metal sulfide or poiysulfide.

4. The process of claim 3 wherein the sulfide or polysulfide is sodium sulfide, sodium polysulfide, potassium sulfide or potassium polysulfide.

5. The process of claim 4 wherein R is alkyl, R is alkyl of l to l2 carbon atoms and R is hydrogen.

6. The process of claim 5 wherein R is alkyl of l to 6 carbon atoms.

'7. The process of claim 6 wherein R and R are methyl.

8. The process of claim 1 wherein R is alkyl, R is alkyl of 1 to 12 carbon atoms and R is hydrogen.

9. The process of claim 8 wherein R and R are methyl. 

1. A PROCESS FOR PREPARING S-METAL SALTS OF N-ACYLPHOSPHOROAMIDOTHIOATES WHICH COMPRISES REACTING AN N-ACYLPHOSPHOROAMIDOTHIOATE OF THE FORMULA
 2. The process of claim 1 wherein the process is conducted in aqueous solution.
 3. The process of claim 2 wherein the sulfide or polysulfide is an alkali metal sulfide or polysulfide.
 4. The process of claim 3 wherein the sulfide or polysulfide is sodium sulfide, sodium polysulfide, potassium sulfide or potassium polysulfide.
 5. The process of claim 4 wherein R1 is alkyl, R2 is alkyl of 1 to 12 carbon atoms and R3 is hydrogen.
 6. The process of claim 5 wherein R2 is alkyl of 1 to 6 carbon atoms.
 7. The process of claim 6 wherein R1 and R2 are methyl.
 8. The process of claim 1 wherein R1 is alkyl, R2 is alkyl of 1 to 12 carbon atoms and R3 is hydrogen.
 9. The process of claim 8 wherein R1 and R2 are methyl. 